All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

Transparent Ultrathin Oxygen‐Doped Silver Electrodes for Flexible Organic Solar Cells

An effective method for depositing highly transparent and conductive ultrathin silver (Ag) electrodes using minimal oxidation is reported. The minimal oxidation of Ag layers significantly improves the intrinsic optical and structural properties of Ag without any degradation of its electrical conductivity. Oxygen‐doped Ag (AgO_x) layers of thicknesses as low as 6 nm exhibit completely 2D and continuous morphologies on ZnO films, smaller optical reflections and absorbances, and smaller sheet resistances compared with those of discontinuous and granular‐type Ag layers of the same thickness. A ZnO/AgO_x/ZnO (ZAOZ) electrode using an AgO_x (O/Ag = 3.4 at%) layer deposited on polyethylene terephthalate substrates at room temperature shows an average transmittance of 91%, with a maximum transmittance of 95%, over spectral range 400?1000 nm and a sheet resistance of 20 Ω sq^?1. The average transmittance value is increased by about 18% on replacing a conventional ZnO/Ag/ZnO (ZAZ) electrode with the ZAOZ electrode. The ZAOZ electrode is a promising bottom transparent conducting electrode for highly flexible inverted organic solar cells (IOSCs), and it achieves a power conversion efficiency (PCE) of 6.34%, whereas an IOSC using the ZAZ electrode exhibits a much lower PCE of 5.65%.     

Approach for Al2O3 rear surface passivation of industrial p‐type Si PERC above 19%

Atomic layer deposition (ALD) of thin Al₂O₃ (≤10 nm) films is used to improve the rear surface passivation of large‐area screen‐printed p‐type Si passivated emitter and rear cells (PERC). A blister‐free stack of Al₂O₃/SiO_x/SiN_x is developed, leading to an improved back reflection and a rear recombination current (J_0,rear) of 92 ± 6 fA/cm². The Al₂O₃/SiO_x/SiN_x stack is blister‐free if a 700°C anneal in N₂ is performed after the Al₂O₃ deposition and prior to the SiO_x/SiN_x capping. A clear relationship between blistering density and lower open‐circuit voltage (V_OC) due to increased rear contacting area is shown. In case of the blister‐free Al₂O₃/SiO_x/SiN_x rear surface passivation stack, an average cell efficiency of 19.0% is reached and independently confirmed by FhG‐ISE CalLab. Compared with SiO_x/SiN_x‐passivated PERC, there is an obvious gain in V_OC and short‐circuit current (J_SC) of 5 mV and 0.2 mA/cm², respectively, thanks to improved rear surface passivation and rear internal reflection. Copyright © 2012 John Wiley & Sons, Ltd.     

Fully Transparent p‐MoTe2 2D Transistors Using Ultrathin MoOx/Pt Contact Media for Indium‐Tin‐Oxide Source/Drain

Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe₂ FETs with oxygen (O₂) plasma‐induced MoO_x/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O₂ plasma and ultrathin Pt‐deposition processes on MoTe₂ surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm² V^?1 s^?1, a high ON/OFF current ratio of ≈10⁵, and 70% transmittance. In particular, for normal MoTe₂ FETs without ITO, O₂ plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm² V^?1 s^?1), introducing ultrathin MoO_x between Pt source/drain and MoTe₂. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.     

Highly Robust Indium‐Free Transparent Conductive Electrodes Based on Composites of Silver Nanowires and Conductive Metal Oxides

A hybrid approach for the realization of In‐free transparent conductive layers based on a composite of a mesh of silver nanowires (NWs) and a conductive metal‐oxide is demonstrated. As metal‐oxide room‐temperature‐processed sol–gel SnO_x or Al:ZnO prepared by low‐temperature (100 °C) atomic layer deposition is used, respectively. In this concept, the metal‐oxide is intended to fuse the wires together and also to “glue” them to the substrate. As a result, a low sheet resistance down to 5.2 Ω sq^‐1 is achieved with a concomitant average transmission of 87%. The adhesion of the NWs to the substrate is significantly improved and the resulting composites withstand adhesion tests without loss in conductivity. Owing to the low processing temperatures, this concept allows highly robust, highly conductive, and transparent coatings even on top of temperature sensitive objects, for example, polymer foils, organic devices. These Indium‐ and PEDOT:PSS‐free hybrid layers are successfully implemented as transparent top‐electrodes in efficient all‐solution‐processed semitransparent organic solar cells. It is obvious that this approach is not limited to organic solar cells but will generally be applicable in devices which require transparent electrodes.     

ZnO Thin Film, Device, and Circuit Fabrication using Low-Temperature PECVD Processes

We report undoped ZnO films deposited at low temperature (200°C) using plasma-enhanced chemical vapor deposition (PECVD). ZnO thin-film transistors (TFTs) fabricated using ZnO and Al₂O₃ deposited in situ by PECVD with moderate gate leakage show a field-effect mobility of 10 cm²/V s, threshold voltage of 7.5 V, subthreshold slope <1 V/dec, and current on/off ratios >10⁴. Inverter circuits fabricated using these ZnO TFTs show peak gain magnitude (dV _out/dV _in) ~5. These devices appear to be strongly limited by interface states and reducing the gate leakage results in TFTs with lower mobility. For example, ZnO TFTs fabricated with low-leakage Al₂O₃ have mobility near 0.05 cm²/V s, and five-stage ring-oscillator integrated circuits fabricated using these TFTs have a 1.2 kHz oscillation frequency at 60 V, likely limited by interface states.     

Thin Al2O3 passivated boron emitter of n‐type bifacial c‐Si solar cells with industrial process

We have presented thin Al₂O₃ (~4 nm) with SiN_x:H capped (~75 nm) films to effectively passivate the boron‐doped p⁺ emitter surfaces of the n‐type bifacial c‐Si solar cells with BBr₃ diffusion emitter and phosphorus ion‐implanted back surface field. The thin Al₂O₃ capped with SiN_x:H structure not only possesses the excellent field effect and chemical passivation, but also establishes a simple cell structure fully compatible with the existing production lines and processes for the low‐cost n‐type bifacial c‐Si solar cell industrialization. We have successfully achieved the large area (238.95 cm²) high efficiency of 20.89% (front) and 18.45% (rear) n‐type bifacial c‐Si solar cells by optimizing the peak sintering temperature and fine finger double printing technology. We have further shown that the conversion efficiency of the n‐type bifacial c‐Si solar cells can be improved to be over 21.3% by taking a reasonable high emitter sheet resistance. Copyright © 2017 John Wiley & Sons, Ltd.     

InGaP/GaAs/Ge triple‐junction solar cells with ZnO nanowires

ZnO nanowire (NW) grown on triple‐junction (TJ) solar cells via the hydrothermal growth method to enhance efficiency is investigated. In this paper, experimental results indicate that TJ solar cells with ZnO NW as an antireflection (AR) coating have the lowest reflectance in the short wavelength spectrum, as compared with those of bare TJ solar cells (without AR coating) and solar cells with SiN_x and TiO₂/Al₂O₃ AR coatings. ZnO NW has the lowest light reflection among all experimental samples, especially in the range of ultraviolet to green light (300–500 nm). It was found that ZnO NW could enhance the conversion efficiency by 6.92%, as compared with the conventional TJ solar cell. In contrast, SiN_x and TiO₂/Al₂O₃ AR coatings could only enhance the conversion efficiency by 3.72% and 6.46% increase, respectively. The encapsulated results also suggested that the cell with ZnO NW coating could provide the best solar cell performances. Furthermore, all samples are measured at tilt angles of 0°–90° and results show that the solar cells with ZnO NW have the highest efficiency at all tilt angles. Furthermore, a small NW diameter increases light absorption. Copyright © 2012 John Wiley & Sons, Ltd.     

Eclipse Pulsed Laser Deposition for Damage‐Free Preparation of Transparent ZnO Electrodes on Top of Organic Solar Cells

Pulsed laser deposited gallium doped zinc oxide (ZnO:Ga) is reported as transparent top electrode for organic solar cells. In contrast to standard coating techniques, prone to harm organic sublayers and leading to strongly reduced device efficiencies, eclipse pulsed laser deposition (PLD) in argon atmosphere is identified as compatible, nonharmful deposition method for ZnO:Ga, even on top of sensitive organic material. Although PLD is not yet ready for mass production, the experiments reveal and solve crucial process limitations, e.g., droplet impacts, which might be useful also for high yield deposition methods. Optimized ZnO:Ga top electrodes achieve a high mean transparency in the visible spectral range of T_vis = 82.7% and a reasonable sheet resistance of R_S = 83 Ω sq^?1. The organic photovoltaic devices prepared with this electrode obtained an efficiency of η = 2.9%, almost equal to the efficiency of reference samples using a state‐of‐the‐art metal top contact (η = 3.0%). The investigations here demonstrate the successful deposition of transparent conductive oxides as top electrode for organic devices and open a new path towards the combination of metal oxides and organic semiconductors.     

Development of a‐SiOx:H solar cells with very high Voc × FF product

In this study, deposition conditions for making a‐SiO_x:H are investigated systematically in order to obtain a high band gap material. We found that at given optical band gap, a‐SiO_x:H with favorable opto‐electronic properties can be obtained when deposited using low CO₂ flow rates and deposition pressures. We also found that a low radio frequency power density is required in order to limit the effect of ion bombardment on the material properties of i‐a‐SiO_x:H and thereby the solar cell performance. In addition, by decreasing the heater temperature from 300 to 200°C when making the i‐a‐SiO_x:H, the V_oc can be increased. We employed optimized p‐doped and n‐doped a‐SiO_x:H films into the p‐i‐n solar cells, and as a consequence, a high V_oc of over 1 V and high fill factor (FF) are obtained. When depositing on texture‐etched ZnO:Al substrates, a high efficiency a‐SiO_x:H single junction solar cell having a high V_oc × FF product of 0.761 (V_oc: 1.042 V, J_sc: 10.3 mA/cm², FF: 0.73, efficiency: 7.83%) was obtained. The a‐SiO_x:H solar cell shows comparable light degradation characteristics to standard a‐Si:H solar cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhanced infrared transmission of GZO film by rapid thermal annealing for Si thin film solar cells

Ga doped ZnO (GZO) films prepared by sputtering at room temperature were rapid thermal annealed (RTA) at elevated temperatures. With increasing annealing temperature up to 570°C, film transmission enhanced significantly over wide spectral range especially in infrared region. Hall effect measurements revealed that carrier density decreased from ∼8 × 10²⁰ to ∼ 3 × 10²⁰ cm⁻³ while carrier mobility increased from ∼15 to ∼28 cm²/Vs after the annealing, and consequently low film resistivity was preserved. Hydrogenated microcrystalline Si (µc‐Si:H) and microcrystalline Si_1‐xGe_x (µc‐Si_1‐xGe_x:H, x = 0.1) thin film solar cells fabricated on textured RTA‐treated GZO substrates demonstrated strong enhancement in short‐circuit current density due to improved spectral response, exhibiting quite high conversion efficiencies of 9.5% and 8.2% for µc‐Si:H and µc‐Si_0.9Ge_0.1:H solar cells, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Highly conductive ZnO films with high near infrared transparency

We present an approach for deposition of highly conductive nominally undoped ZnO films that are suitable for the n‐type window of low band gap solar cells. We demonstrate that low‐voltage radio frequency (RF) biasing of growing ZnO films during their deposition by non‐reactive sputtering makes them as conductive as when doped by aluminium (ρ≤1·10⁻³Ω cm). The films prepared with additional RF biasing possess lower free‐carrier concentration and higher free‐carrier mobility than Al‐doped ZnO (AZO) films of the same resistivity, which results in a substantially higher transparency in the near infrared region (NIR). Furthermore, these films exhibit good ambient stability and lower high‐temperature stability than the AZO films of the same thickness. We also present the characteristics of Cu(InGa)Se₂, CuInSe₂ and Cu₂ZnSnSe₄‐based solar cells prepared with the transparent window bilayer formed of the isolating and conductive ZnO films and compare them to their counterparts with a standard ZnO/AZO bilayer. We show that the solar cells with nominally undoped ZnO as their transparent conductive oxide layer exhibit an improved quantum efficiency for λ > 900 nm, which leads to a higher short circuit current density J_SC. This aspect is specifically beneficial in preparation of the Cu₂ZnSnSe₄ solar cells with band gap down to 0.85 eV; our champion device reached a J_SC of nearly 39 mAcm⁻², an open circuit voltage of 378mV, and a power conversion efficiency of 8.4 %. Copyright © 2015 John Wiley & Sons, Ltd.     

Laser‐fired contact optimization in c‐Si solar cells

In this work we study the optimization of laser‐fired contact (LFC) processing parameters, namely laser power and number of pulses, based on the electrical resistance measurement of an aluminum single LFC point. LFC process has been made through four passivation layers that are typically used in c‐Si and mc‐Si solar cell fabrication: thermally grown silicon oxide (SiO₂), deposited phosphorus‐doped amorphous silicon carbide (a‐SiC_x/H(n)), aluminum oxide (Al₂O₃) and silicon nitride (SiN_x/H) films. Values for the LFC resistance normalized by the laser spot area in the range of 0.65–3 mΩ cm² have been obtained. Copyright © 2011 John Wiley & Sons, Ltd.     

Zr‐Doped Indium Oxide (IZRO) Transparent Electrodes for Perovskite‐Based Tandem Solar Cells

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm² V^?1 s^?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □^?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In₂O₃) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm^?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.     

Si/Al2O3/ZnO:Al capacitor arrays formed in electrochemically etched porous Si by atomic layer deposition

High surface area Si/Al₂O₃/ZnO:Al capacitors were formed in electrochemically etched porous silicon. The Al₂O₃ dielectric and the ZnO:Al top electrode were deposited by atomic layer deposition in high aspect ratio porous Si. A single capacitor with a typical area of about 1 mm² consisted of about 10⁵ pores. Effective capacitance densities were between 2.0 and 2.5 μF/cm², i.e., approximately 30 times higher than for a planar capacitor prepared under identical conditions, illustrating the effect of the enhanced surface area in the porous structure.     

Nonfullerene Electron Transporting Material Based on Naphthalene Diimide Small Molecule for Highly Stable Perovskite Solar Cells with Efficiency Exceeding 20%

This study reports a new nonfullerene electron transporting material (ETM) based on naphthalene diimide (NDI) small molecules for use in high‐performance perovskite solar cells (PSCs). These solar cells simultaneously achieve high power conversion efficiency (PCE) of over 20% and long‐term stability. New NDI‐ID (N,N′‐Bis(1‐indanyl)naphthalene‐1,4,5,8‐tetracarboxylic diimide) consisting of an N‐substituted indane group having simultaneous alicyclic and aromatic characteristics is synthesized by a low‐cost, one‐step reaction, and facile purification method. The partially flexible characteristics of an alicyclic cyclopentene group on indane groups open the possibility of low‐temperature solution processing. The conformational rigidity and aromaticity of phenyl and alicyclic groups contribute to high temporal stability by strong secondary bonds. NDI‐ID has herringbone packed semiconducting NDI cores that exhibit up to 0.2 cm² V^?1 s^?1 electron mobility in field effect transistors. The inverted PSCs based on CH(NH₂)₂PbI_3–xBr_x with NDI‐ID ETM exhibit very high PCEs of up to 20.2%, which is better than that of widely used PCBM (phenyl‐C61‐butyric acid methyl ester) ETM‐based PSCs. Moreover, NDI‐ID‐based PSCs exhibit very high long‐term temporal stability, retaining 90% of the initial PCE after 500 h at 100 °C with 1 sun illumination without encapsulation. Therefore, NDI‐ID is a promising ETM for highly efficient, stable PSCs.     

Improved Interface and Electrical Properties by Inserting an Ultrathin SiO2 Buffer Layer in the Al2O3/Si Heterojunction

An ultrathin SiO₂ interfacial buffer layer is formed using the nitric acid oxidation of Si (NAOS) method to improve the interface and electrical properties of Al₂O₃/Si, and its effect on the leakage current and interfacial states is analyzed. The leakage current density of the Al₂O₃/Si sample (8.1 × 10^?9 A cm^?2) due to the formation of low‐density SiO_x layer during the atomic layer deposition (ALD) process, decreases by approximately two orders of magnitude when SiO₂ buffer layer is inserted using the NAOS method (1.1 × 10^?11 A cm^?2), and further decreases after post‐metallization annealing (PMA) (1.4 × 10^?12 A cm^?2). Based on these results, the influence of interfacial defect states is analyzed. The equilibrium density of defect sites (N_d) and fixed charge density (N_f) are both reduced after NAOS and then further decreased by PMA treatment. The interface state density (D_it) at 0.11 eV decreases about one order of magnitude from 2.5 × 10¹² to 7.3 × 10¹¹ atoms eV^?1 cm^?2 after NAOS, and to 3.0 × 10¹⁰ atoms eV^?1 cm^?2 after PMA. Consequently, it is demonstrated that the high defect density of the Al₂O₃/Si interface is drastically reduced by fabricating ultrathin high density SiO₂ buffer layer, and the insulating properties are improved.     

Deposition of aluminum oxide-doped zinc oxide transparent nano-films on glass substrates for electrostatic discharge applications

Aluminum oxide-doped zinc oxide (ZnO:Al₂O₃) transparent thin films were deposited by DC magnetron sputtering on glass substrates; film thickness can be correlated with deposition time. The effect of ZnO:Al₂O₃ film thickness on electrical properties, ultraviolet (UV) transmission, surface morphology and structure, solvent resistance, and scratch hardness was investigated. The surface roughness and crystallite size of deposited films increased from 0.75 to 2.22 nm and from 14 to 57 nm, respectively, as the film thickness was increased from 18 to 112 nm. In contrast, the percent UV transmission (% T) of ZnO:Al₂O₃ deposited glass plates at a wavelength of 365 nm increased when the film thickness was decreased. The electrical properties of nano-film deposited glass plates such as electrical resistance, tribo-charge voltage, and decay time were in the range of electrostatic discharge (ESD) specifications. The ZnO:Al₂O₃ nano-film deposited glass substrate possessed good acetone and iso-propanol resistance as well as high scratch hardness. This work opens up the possibility of using the ZnO:Al₂O₃ transparent ultra-thin film on glass substrate in ESD applications based on their excellent properties in terms of the relatively thin and adjustable ZnO:Al₂O₃ film thickness needed.